Diphenylamine azo dyestuffs



Patented Jan. 1, 1946 umrso STATES PATENT o-Fncs DIBHENYLAMINE AZODYESTUFFS Robert P: Parker, S'omerville, and Cori-is Mabelle Hofr'na-nn, Bound Brook, N. J assignors to American- Cyanamid Company, New York, N. 2., acorporation of Maine Nanmw na. Alir c n lulx t flia.

SQ ia UN 3 31 in-which It stands for= the radical: of- 'a coupling component;

the nitroso derivativeas this product giyes duller and less desirable shades on coupling. However, itis possible to hydrolyz theN-hitrosodyes ffs in; dilute solution by heating with alkalies such as soda ash. If desired, reducin agents such as sodium sulfide, o sodium bisulfite'and the; like .may be included-in thehyd-rolysis; step in,order to destroy nitric oxides as they, ar liberated.

In the past there: has been a demand for ice-- colors having strongblue to violet shades. Many attempts have-been made'to produce such dyestufis and in many-cases the fastness properties such as fastness to light, heat and washingi have left'much to be desired. It-is anadvantageofvthe present invention" that ice-colorsof strong blue to violet shades can be produced which as pigmentsior dyes exhibit superior fastness properties such. as, fastness to light, heat and washing;

The present, invention is not. limited to icecolors as the tetrahydrofurfuryloxy amino diphenylamine after diazotization may be coupled witha variety of other coupling components suchzias: for x mple, th se, o ta nin s lub li ins; roups producing dyestu s: which, are 0 ubl'e in water; and; which; are; capa l Ofr dyei as acid: or direct dyestufi's; The; ice-colors producible by the present. invention, aretparticularly outstanding in their properties-andtherefore constitutethe preferred embodiment, of the present invention:-

The present invention is, ofacoursenot 0 1-1? cemed with; the process used inpreparingthe ,1 die phenylamines. These; compounds and a. process; ofi'making them form a subject. matter; of ounce,- pending: application Serial No. 543,436; filed July 3', 1 944. In general, they may.- be prepared; by reacting:'M-hydroxyAmitro; diphenylamine-with attetrahydrofurfuryli esterin the presence of; an acid binding substance following: by reduction of the nitro grou in acidor alkalin medium, the pH determiningwhether the compound is obtained in the form of the free base or a salt thereof. 1

In the process of diazotization higher temperature; greater concentration of, the base and higher mineral and nitrous acid concentrations tend to produce the N-nitroso derivative of the diazonium salts, while, at. lowerv temperature, lower In their diazotiz ed form, thesebasesmay be coupled either with or without a, substrate, to yield dyestufis or pigmentsof reat valuejbe cause of their strength, varietyof s'hadeiandf -ast; nessproperties; In, particular. however, these bases are important for the production. of fast b ue.- rin or y i gs u n cenlulosic' ma e als which are the preferred form of. the present in;

:vention. 'Ifhese are produced in general, byimpregnating; the cellulosic material alkaline baths with, appropriate, ice-color oollplingi com on h s and h n.hr nt ne l t he d1 ized ses whi hav r e e d and. t ick: re u n: u h P ha d c o h, or by. y in he pre a ed; thb f d olutions o he diazotized; bases.

o utio s, o e d a o i-z s es ito r?- e e pr c o he pre nt nveh oh, ma also be treated with inorganic alkali metal salts or alkaline-earth metal salts, or with, mixtures of, these salts; together with appropriate inorganic metal salts whereupon the diazoniurn salts or metal salt complexes, of the diazonium salts are p c pi te h s may h v pa a ed, ried, stored or blendedwith inor anic salts. such, for example, as with sodium or potassium, chlorides, sulfates, magnesilnn sulfate, aluminum suliate and the like; the latter preferably beingused in their partially dehydrated fprms. 'Suchproducts may be readily dissolved in water to yield solutions from which cellulosic materials which have previouslybeen impregnatedin alkaline; ground- 7 ing baths with appropriate ice-color coupling components may be; suitably pad dyed, or the solutions may be appropriately thickened and r n e u on, he pr pa d ellulos a r c e b s us d n t e Pr en hy h a r mar also be converted int a diazo;sulfonate which fi r d h nt d o edb treatment acideoncentration and by slower addition otni with steam, or by steam in the presence of weal; acid vapors.

ubstantially any of the ice-color, oohpling components are generally useful for production of insoluble, developed dyes, and enable the @production of a variety of colors from yellow to blue. However, for the present purposes, the use of arylides of 2-hydroxy-3-naphthoic acid is preferable. 'I'hese produce, when coupled with thediazotized bases under the present invention, the most desirable blue to violet shades.

However, the invention is not necessarily so limited. Among other ice-color coupling com ponents which produce useful products may be. listed by way of example such compounds as beta- 1 naphthol, 8'-amino-2-naphthol, 8'-acetyl-am'in'o- 1 '2-naphthol, benzoyl naphthols; pyrazolones and pyrazyl pyrazolones; hydroxy benzofiuorenones; 'hydroxy derivatives of phenyl naphthyla nines V such as 7-hydroxy-l-naphthyl-m-hydroxyphenyl amine; the various N-substituted amide such "as Example 2 cmc m 9.4 parts of the nitro compound as obtained in Example 1 are stirred together with 17.8 parts of alcohol and 36.9 parts of a 45% sodium sulihydrate solution and the whole is refluxed until reductioniscomplete. The addition of 75 parts of water precipitates an oil which is extracted with ether. The ether' extract is separated from the arylides of 5,6,7,8-tetrahydro-2-hydroxy-3-naphthoic acid, of 2-hydroxy-3-anthroic acid, of

methyl and dimethyl salicyclic acids, of 'hydroxy carbazole carboxylic acids, of hydroxy benzocarbazole carboxylic acids, of hydroxy-benzoacridone carboxylic acids, of 3,7-dihydroxy naphthalene- 2,6-dicarboxylic acid, of hydroxy-dibenz'ofuran carboxylic acids, of hydroxy behzothiophene'caiboxylic' acids, etc., and t e arylides of acetoacetic acid, furoyl acetic acid, benzoylacetic acid,

terephthaloyl-bis-acetic acid and the like. fThe I arylide group in the coupling component may be a simple aromatic group such as the radicalf anilin'eor of an aniline derivative'or of a naphthylamine,.or it maybe the radical'of a heterocyclic amine, such as, e. g.,-of an amine of the benj zothiazole series or of a diamine of the diphenyl ene sulfone series. I

".Thebases of the present invention also may be has none. Illustrative examples-oi such coupling components include salicyclic acid, resorcinol, m-

3 usedin the preparation of water-solubledyestufis 1 suitable for dyeing vegetable or animal fibers. In this case; a great many of the customary phenolic or aminic couplingcomponentsmay be used. The t 7 coup n omponent, however, must carry atleast one sulfonic group in case the diazo component i phenylenejdiamine, the large number of naphtholsulfonic acids such as e. g., Racid, G acid,-the

Cleves'acids, J acid, gammaacid, J -acid urea and J-acid imide, H-acid and many others. Pyraz olones such assulfonic derivativesof l-phenyl 3- methyl Dyrazolone-B. also may be used.

. vThe invention will bemore fully illustrated in conjunction with'the following examples which are meant to be illustrative only andfnot by way 1 offlim'itation. All'parts are by weight unless otherwise noted. 7

,3 0i .4'ehydroxy- 4-nitro' diphenylamine a are. dissolved in 5Q parts of Water by the addition of 4'.4 parts of sodium hydroxidein a; suitable reaction vessel and'the solutionis heated to reflux temperature. 2 8.2 partsof tetrahydrofurfuryl para-toluene sulionate are dropped in slowly and the reaction is completed by refluxing for four hours. The reaction mixture is cooled andthe i- 'tetrahydrofurfuryloxyi-nitro diphenylamine is allowed to settle. jThe supernatant liquor is re- V moved and the, crude productj 9f um' i t purity for, direct use. H

I on a steam bath, .is filtered. oil, is hot water and is dried at 55? C. I

-2 parts of the blended diazonium 'chlorid pared as described in Exampl 4 are dissolved in reduction mixture, is washed by decantation with water and isithen treated with 3 parts of concentrated sulfuric acid. 7 An oil is precipitated'from the ether solution which is separated and is dissolved in 125 parts of water. After clarification of the aqueous solution in the presence of decolorizing carbon, theneutral sulfate of lQ-tetrahyis complete. 'The'resulting diazo'solution is clarified by filtration in the presence of decolorizing carbon at 40 C. and the resultingfiltrate is treated with sodium chloride. The precipitated diazonium chloride derived'from 4'-tetrahydro furfuryloxy-4-amino-diphenylamine is separated by filtration and is dried at low temperature,

E am l 2.3 parts of the dry diazonium chlorideob tained as described in Example 3 are blended 'by grinding with one part ofrmag'ne'sium sulfate dihydrate and one part'of anhydrous 'sodium sulfate toahomogeneouspowder. 0.4 part of this'col'or blend is"sti'rred in 2.5

parts of methanol and the slurry is treated with a mixture of 1.5 parts of. beta-naphthol in 2.5 parts of methanol containing 5.0 partsfiof'py'ridine. Themixture changes to a deep blue-black slurry immediately and a thick paste results. This is stirred while heated on asteam bath .rfor 10 minutes and is thendiluted with. 300 parts of water and the solution is madealk'aline with 10 parts of 20% sodium hydroxide solution. The precipitated. pigment is fiocculated' bydigestion washed with 'A deep blue-black powder results-insoluble in water. I

Example 5 pre- 28 partsof waterand the solution is thickened byYthe addition of partsfof ja suitable car bohydrate thickener. The printing paste" is printed on cotton piece goods previouslyimpreg nated with'the anilide-of 2-hydroxy-3 naphthoic acid by the customary procedurein'an alkaline assent bathythe print-is dried, is cleared-in a soda ash solution at 70 C., is soaped at 650; in a 1 /2 soap solution, rinsed anddried.

The pattern is printed a bright blue of very good fastness properties.

Example 6 The blended diazonium chlorideas; prepared in Example 4 is used to produce developed dyeings on cotton fabric by the following procedure:

Cotton fabric is treated in alkaline grounding baths comprising parts or ice color coupling component; -5 parts off methanol; parts of 20% sodium hydroxide solution and 470 parts of Water. The treated cloth is passed between squeeze rolls and is immediately dried at 65 C.

5 parts of a fabric so treated is entered in a dye bath containing 0.3 part of the dry blended mixture of diazoni-um chloride dissolved in 150 parts of water and while the fabric is efliciently agitated, 5 parts of 20% sodium acetate solution are run in.

When flull color development is obtained, the fabric is rinsed in warm water, is cleared at 70 C. in an alkaline solution (3% soda ash and 2% sodium hydroxide) for 2 minutes, then treated at 70 C. in a /2% soap solution, rinsed in fresh water and dried.

The colors obtained with various ice color coupling components are listed below:

Coupling component Color Reddish shade of blue.

Strong greenish blue.

Golden yellow. Purple.

am e Bis-(acetoecetic)-ortho4zolidide 2-hydroxy-3-cerbazole carboxylic acid-(2- methyl anilide) 2-hydrexy-3-naphthoie acid-(4-ch1oroan Bright greenish blue.

ilide Example 7 NaOaS diazotized by the slow addition of 3.5 parts of 10% sodium nitrite solution.

1.4 parts of 5,5-dihydroxy-2,2'-dinaphthylurea-'7,7-disulfonic acid are dissolved in 40 parts of water and 3.1 parts of soda ash are dissolved in the solution. The temperature is adjusted at 10 C. and the above prepared diazo solution is slowly dropped in with efficient agitation. Coupling is immediate with the formation of a deep blue color. The solution is treated with sodium j chloride until the dyestuff is completely salted out and the dyestuff is isolated by filtration.

Afterdrying at 40 C., a deep blue-black solid is obtained which is readily soluble in water, yielding a blue solution.

Example 8 0.5 part of the dyestuff as obtained in Example 7 is dissolved in 500 parts of water. parts of this standard solution are dilutedwi-th 25Q'parts of water and 3.5 parts of 10% Glaubers salt 1 part of 10% sulfuric aeidare'added. 5 parts of az'woolen skein are; well boll-ed out in 1% soap solution, rinsedin, fresh water, wrung out and entered, into this dye bath. The temperature is raised to the boil and is maintainedthus for one hour while the woolen slrein is well agitated. After removal from th dyebath, the wool is rinsed in hot water, soapedi-n /2% soapsolution at. 65; ns d again a d fina y, dried.

The skein is levelly dyed a royal blue-M dis. tinctive brightness.

Example 9,

50 parts of the standard dye solution prepared as described in Examplefi" are di1uteds'with'150 parts of water and 15 parts of a 10 sodium chloride solution are added. 5 parts of a previously wet out cotton skein are entered into this dye bath and are agitated efliciently while the temperature is slowly raised to the boil. The dye bath is maintained at the boil until color development is complete as is indicated by exhaustion of the dye bath. The skein is removed, is rinsed, treated at 65 C. in a 1% soap solution, again rinsed and I dried.

The skein is evenly dyed a bright greenish blue shade of excellent wash and light fastness.

We claim:

1. Azo coloring matter having the following formula.

in which A is the residue of a coupling component.

CHr-OH:

2. Azo coloring matter having the following formula:

in which A is the residue of an ice coupling component.

3. Azo coloring matter having the following formula:

O O NH-Ar in which Ar is aryl. 

